Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes

Holming F. Yuen; Tobin J. Marks

doi:10.1021/om7008952

Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes

Holming F. Yuen, Tobin J. Marks

Northwestern University

Research output: Contribution to journal › Article › peer-review

65 Citations (Scopus)

Abstract

Using base-free Ln[N(SiHMe₂)₂]₃ complexes as highly effective protodeamination reagents, the binuclear lanthanide complexes p-bis{η⁵-(2,3,4,5-tetramethylcyclo-pentadienyl) Ln[N(SiHMe₂)₂]₂}phenylene [p-Ln₂] (Ln -Y, La, Lu) and m-bis{η⁵-(2,3,4,5- tetramethylcyclopentadienyl)La-[N(SiHMe₂)₂] ₂}phenylene [m-La₂] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serve as new types of multicenter homogeneous 4f catalysts. Reactivity studies reveal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnover frequencies as high as 10 h ^-1 at 60°C.

Original language	English
Pages (from-to)	155-158
Number of pages	4
Journal	Organometallics
Volume	27
Issue number	2
DOIs	https://doi.org/10.1021/om7008952
Publication status	Published - Jan 28 2008

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes",

abstract = "Using base-free Ln[N(SiHMe2)2]3 complexes as highly effective protodeamination reagents, the binuclear lanthanide complexes p-bis{η5-(2,3,4,5-tetramethylcyclo-pentadienyl) Ln[N(SiHMe2)2]2}phenylene [p-Ln2] (Ln -Y, La, Lu) and m-bis{η5-(2,3,4,5- tetramethylcyclopentadienyl)La-[N(SiHMe2)2] 2}phenylene [m-La2] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serve as new types of multicenter homogeneous 4f catalysts. Reactivity studies reveal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnover frequencies as high as 10 h -1 at 60°C.",

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AU - Yuen, Holming F.

AU - Marks, Tobin J.

PY - 2008/1/28

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N2 - Using base-free Ln[N(SiHMe2)2]3 complexes as highly effective protodeamination reagents, the binuclear lanthanide complexes p-bis{η5-(2,3,4,5-tetramethylcyclo-pentadienyl) Ln[N(SiHMe2)2]2}phenylene [p-Ln2] (Ln -Y, La, Lu) and m-bis{η5-(2,3,4,5- tetramethylcyclopentadienyl)La-[N(SiHMe2)2] 2}phenylene [m-La2] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serve as new types of multicenter homogeneous 4f catalysts. Reactivity studies reveal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnover frequencies as high as 10 h -1 at 60°C.

AB - Using base-free Ln[N(SiHMe2)2]3 complexes as highly effective protodeamination reagents, the binuclear lanthanide complexes p-bis{η5-(2,3,4,5-tetramethylcyclo-pentadienyl) Ln[N(SiHMe2)2]2}phenylene [p-Ln2] (Ln -Y, La, Lu) and m-bis{η5-(2,3,4,5- tetramethylcyclopentadienyl)La-[N(SiHMe2)2] 2}phenylene [m-La2] were synthesized from the corresponding phenylene-linked tetramethylcyclopentadienes. The resulting products serve as new types of multicenter homogeneous 4f catalysts. Reactivity studies reveal that these binuclear organolanthanide complexes efficiently catalyze the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminodienes, with turnover frequencies as high as 10 h -1 at 60°C.

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Synthesis and catalytic properties of phenylene-bridged binuclear organolanthanide complexes

Abstract

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